S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB...S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.展开更多
随着工业化进程的加快和城市化的发展,大量污染物排入黄河流域,并被频繁检出,威胁生态系统和人类健康。为获取潜在生态环境风险污染物,该研究通过调研2000年1月1日−2022年12月31日Web of Science(WoS)和中国知网(CNKI)数据库中黄河流域...随着工业化进程的加快和城市化的发展,大量污染物排入黄河流域,并被频繁检出,威胁生态系统和人类健康。为获取潜在生态环境风险污染物,该研究通过调研2000年1月1日−2022年12月31日Web of Science(WoS)和中国知网(CNKI)数据库中黄河流域已报道的288篇污染物相关文献,使用多指标综合评分法筛选黄河流域的特征污染物,采用风险商值法获取水样和沉积物中的风险污染物。结果表明:①黄河流域共检出10类144种污染物,采用9类共13个筛选指标构建多指标综合评分法,对污染物各项指标进行评分,然后进行K-means聚类分析,按得分高低分为Ⅰ~Ⅵ级,选取得分较高的33种Ⅰ级和Ⅱ级高分值污染物作为黄河流域特征污染物,包括12种有机氯农药、10种多环芳烃、10种多氯联苯和1种邻苯二甲酸酯。②水样污染物浓度和沉积物含量前5种都是重金属、有机氯农药、邻苯二甲酸酯、多环芳烃以及药品和个人护理产品,而且二者顺序完全一致,且多数污染物的浓度之间存在显著相关性。③根据风险最大化原则,使用风险商值法(RQ)分别对水样和沉积物进行风险评估,将RQ≥0.1的污染物列为风险污染物,水样中共筛选出21种风险污染物,其中RQ≥1的高风险污染物有5种,包括硒、铅、苯并[a,h]蒽、苯并[a]蒽和邻苯二甲酸二丁酯。④沉积物中共筛选出19种风险污染物,其中有13种高风险污染物,包括8种多环芳烃(芘、蒽、荧蒽、苊、萘、芴、苯并[a]蒽、苯并[a,h]蒽)、4种重金属(汞、铅、硒、砷)和1种邻苯二甲酸酯(邻苯二甲酸二丁酯)。该研究对相关部门拟定黄河流域污染物监测方案和管控措施有重要参考意义。展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.51602018 and 51902018)the Natural Science Foundation of Beijing Municipality(No.2154052)+3 种基金the China Postdoctoral Science Foundation(No.2014M560044)the Fundamental Research Funds for the Central Universities(No.FRF-MP-20-22)USTB Research Center for International People-to-people Exchange in Science,Technology and Civilization(No.2022KFYB007)Education and Teaching Reform Foundation at University of Science and Technology Beijing(Nos.2023JGC027,KC2022QYW06,and KC2022TS09)。
文摘S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.
文摘随着工业化进程的加快和城市化的发展,大量污染物排入黄河流域,并被频繁检出,威胁生态系统和人类健康。为获取潜在生态环境风险污染物,该研究通过调研2000年1月1日−2022年12月31日Web of Science(WoS)和中国知网(CNKI)数据库中黄河流域已报道的288篇污染物相关文献,使用多指标综合评分法筛选黄河流域的特征污染物,采用风险商值法获取水样和沉积物中的风险污染物。结果表明:①黄河流域共检出10类144种污染物,采用9类共13个筛选指标构建多指标综合评分法,对污染物各项指标进行评分,然后进行K-means聚类分析,按得分高低分为Ⅰ~Ⅵ级,选取得分较高的33种Ⅰ级和Ⅱ级高分值污染物作为黄河流域特征污染物,包括12种有机氯农药、10种多环芳烃、10种多氯联苯和1种邻苯二甲酸酯。②水样污染物浓度和沉积物含量前5种都是重金属、有机氯农药、邻苯二甲酸酯、多环芳烃以及药品和个人护理产品,而且二者顺序完全一致,且多数污染物的浓度之间存在显著相关性。③根据风险最大化原则,使用风险商值法(RQ)分别对水样和沉积物进行风险评估,将RQ≥0.1的污染物列为风险污染物,水样中共筛选出21种风险污染物,其中RQ≥1的高风险污染物有5种,包括硒、铅、苯并[a,h]蒽、苯并[a]蒽和邻苯二甲酸二丁酯。④沉积物中共筛选出19种风险污染物,其中有13种高风险污染物,包括8种多环芳烃(芘、蒽、荧蒽、苊、萘、芴、苯并[a]蒽、苯并[a,h]蒽)、4种重金属(汞、铅、硒、砷)和1种邻苯二甲酸酯(邻苯二甲酸二丁酯)。该研究对相关部门拟定黄河流域污染物监测方案和管控措施有重要参考意义。
